CN103951604B - A kind of method of indoles Separation ＆ Purification - Google Patents
A kind of method of indoles Separation ＆ Purification Download PDFInfo
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- CN103951604B CN103951604B CN201410142972.4A CN201410142972A CN103951604B CN 103951604 B CN103951604 B CN 103951604B CN 201410142972 A CN201410142972 A CN 201410142972A CN 103951604 B CN103951604 B CN 103951604B
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- indoles
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- reextraction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
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- Organic Chemistry (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of indoles Separation ＆ Purification, to utilize the kettle Residual oil after the extraction β methyl naphthalenes of the mixed methylnaphthalene of indoles content 4~6% or indoles content 8~30%, it is mixed by a certain percentage with nonpolar solvent, then single extraction is carried out to get to the heavy phase rich in indoles and the light phase containing a small amount of remaining indoles with polar solvent；It is added a certain proportion of water in heavy phase, then reextraction is carried out to get to 85% or more indoles content with the heavy phase of nonpolar solvent pair plus water（Corresponding to mixed methylnaphthalene raw material）Or 99% or more（Corresponding to kettle residual feedstocks）Heavy phase（When finger disregards solvent content）；Then the rectifying that the obtained heavy phase of reextraction carries out is detached to get to the indoles finished product of the thick indoles of polar solvent and 85% or more indoles content without indoles or 99% or more indoles content.The technical process is simple, and flow is short, and the indoles rate of recovery is high, and production cost is low.
Description
Technical field
The present invention relates to a kind of methods of the indoles Separation ＆ Purification of field of coal tar deep processing, specifically, being related to one
The method of kind Separation ＆ Purification indoles from the kettle Residual oil after mixed methylnaphthalene or extraction beta-methylnaphthalene.
Background technology
About the extraction process of indoles, have many patents or documents and materials, wherein being typically include：Application number
200410066250.1 that mentions uses solvent pairs（Polar solvent and nonpolar solvent）Extraction and separation indoles, highly efficient distilling purify Yin
The method of diindyl；Water perseverance good fortune etc. exists《Coal tar is detached and is refined》In mention, can in polar solvent plus water with improve indoles extraction
The selectivity for taking process, it is similar with the method that application number 200410066250.1 is mentioned；Application number 200410066247.X is proposed
The method of the separating indole of saline extraction, by the aqueous solution of alcohol, glycol or alcamines plus the method for salt is to improve molten
Agent is to the selectivity of indoles, to improve indoles content in extraction phase（When referring to the content for disregarding solvent and salt, similarly hereinafter）, to reduce
Follow-up indoles rectifying separating difficulty.
The above-mentioned published patent application materials and previous patent are mainly concentrated in the selectivity by improving solvent,
To improve indoles content in extraction phase or reduce the content of the neutral substances such as methyl naphthalene in extraction phase, to reduce subsequent Yin
Diindyl rectifying separating difficulty.Problem is that anyway, indoles content can only achieve 45 in the above-mentioned obtained extraction phase of separation method
~65%（Corresponding to the mixed methylnaphthalene raw material of indoles content 4~6%）Or 60~80%（Corresponding to the kettle of indoles content 8~30%
Residual feedstocks）, need that indoles content is improved 90~95% by subsequent highly efficient distilling, then doing by solvent crystallization again
Method, to further increase indoles content.Because there is azeotropic in indoles and major impurity, that is, methyl naphthalene therein, biphenyl etc.,
Above-mentioned rectifying is difficult, and yield generally only has 30~60%, and is operated under big reflux ratio, and energy consumption is very high；Equally,
Subsequent crystallization needs devices, the energy consumptions such as freezing, solvent distillation recovery also very high.It is of course also possible to utilize above-mentioned 45~80%
Indoles fraction, to 99% or more, but has no material alterations through a step rectifying in separation principle, and actual recovery is also lower.For
Saline extraction method disclosed in 200410066247.X, as soon as the also inevitable upper reluctant problem of area production,
It is that how salt recycles, salt is heavy corrosion, saline crystallization difficulty of transportation of the high temperature distillation process to equipment the problems such as.It is overall
On say, above-mentioned extracting process there are complex technical process, production procedure is long, equipment investment is big, production cost is high, process yield is low
The problem of, in the upper no practical significance of production, so that so far there are no industrialized report.
Invention content
A certain proportion of water is added in the heavy phase mainly after single extraction in the present invention, then doing by reextraction
The neutral impurities such as method removal methyl naphthalene therein, biphenyl, to directly obtain 85% or more indoles content（Corresponding to mixed methyl
Naphthalene raw material）Or 99% or more（Corresponding to kettle residual feedstocks）Heavy phase（When finger disregards solvent content）.Due to this method process efficiency
Height selects common cheap nonpolar solvent that can reach extraordinary effect, significantly shortens technological process, improve
Process yield makes indoles extractive technique be of practical significance to which production cost be greatly saved, and establishes first set at home
Industrialized unit.
Preferred embodiment is：
Technical solution 1：A kind of method of indoles Separation ＆ Purification, including following steps：Utilize indoles content 3~6%
Mixed methylnaphthalene be raw material, mixed by a certain percentage with nonpolar solvent, then with polar solvent carry out single extraction to get
To the heavy phase rich in indoles and the light phase containing a small amount of remaining indoles；It is added 0.1~0.7 times of water in heavy phase, then with nonpolar
The heavy phase of solvent pair plus water carries out reextraction to get to 85% or more the product of indoles content when disregarding solvent content；Then right
The rectifying that the obtained heavy phase of reextraction carries out detach to get to without indoles polar solvent and 85% or more content it is thick
Indoles.
Technical solution 2：A kind of method of indoles Separation ＆ Purification, including following steps：Using indoles content 8~
Kettle Residual oil after 30% extraction beta-methylnaphthalene is raw material, is mixed by a certain percentage with nonpolar solvent, then uses polar solvent
Single extraction is carried out to get to the heavy phase rich in indoles and the light phase containing a small amount of remaining indoles；0.1~0.7 is added in heavy phase
Times water, then carry out reextraction with the heavy phase of nonpolar solvent pair plus water to get to indoles content 99% when disregarding solvent content
Above heavy phase（；Then the rectifying that the obtained heavy phase of reextraction carries out is detached to get to the polar solvent without indoles
With the indoles finished product of 99% or more content.
The method of the indoles Separation ＆ Purification of technical solution 1 or 2, the polar solvent are triethylene glycol, ethylene glycol, diformazan
Base sulfoxide or ethanol amine；The nonpolar solvent is the kerosene of 160~200 DEG C of boiling point, 200#Solvent naphtha, normal octane or oil
Ether.
The method of the indoles Separation ＆ Purification of technical solution 1 or 2, the polar solvent dosage are the 0.3 of indoles raw material
~1.0 times, the dosage of nonpolar solvent is 0.3~1.5 times of indoles raw material；In the reextraction, the use of nonpolar solvent
Amount is 0.5~3.0 times of heavy phase.
The method of the indoles Separation ＆ Purification of technical solution 1 or 2, the single extraction or reextraction, be all 3~
The counter-current extraction carried out in 20 grades of extraction equipment.
Specific implementation mode
Embodiment 1：
The kettle residual feedstocks of indoles content 8%, with the kerosene of 0.3 times of triethylene glycol and 0.7 times of 160~200 DEG C of boiling point, into
Row single extraction, extraction series is 3 grades, and 0.4 times of water is added in obtained heavy phase, then is carried out with 1.0 times of kerosene secondary
Extraction, extraction series is 4 grades, and gained heavy phase indoles content reaches 99.0%（When finger disregards wherein water and solvent content）, through distillation
Water and solvent are removed up to 99.0% finished product indoles.
Embodiment 2：
The mixed methylnaphthalene raw material of indoles content 3%, with 1.0 times of ethylene glycol and the 200 of 0.3 times#Solvent naphtha carries out primary
Extraction, extraction series is 20 grades, and 0.1 times of water is added in obtained heavy phase, then again with the 200 of 0.5 times#Solvent naphtha row is secondary
Extraction, extraction series is 15 grades, and gained heavy phase indoles content reaches 85.1%（（When finger disregards wherein water and solvent content）, through steaming
Distillation go water and solvent up to 85.1% thick indoles.
Embodiment 3：
The kettle residual feedstocks of indoles content 30% carry out single extraction with 0.7 times of dimethyl sulfoxide (DMSO) and 1.0 times of normal octane,
It is 10 grades to extract series, and 0.7 times of water is added in obtained heavy phase, then carries out reextraction with 1.5 times of normal octane again, extracts
It is 12 grades to take series, and gained heavy phase indoles content reaches 99.3%（When finger disregards wherein water and solvent content）, through water is distilled off
With solvent up to 99.3% finished product indoles.
Embodiment 4：
The kettle residual feedstocks of indoles content 15% carry out single extraction with 1.0 times of ethanol amines and 1.5 times of petroleum ether, extraction
Series is 6 grades, and 0.4 times of water is added in obtained heavy phase, then carries out reextraction with 3.0 times of normal octane again, extracts grade
Number is 7 grades, and gained heavy phase indoles content reaches 99.2%（When finger disregards wherein water and solvent content）, through water and molten is distilled off
Agent up to 99.2% finished product indoles.
Comparative example 1：
Single extraction is carried out by the raw material and condition of embodiment 1, but without reextraction, indoles in obtained heavy phase
Content is 70%（When finger disregards wherein solvent content）, through water and solvent is distilled off up to 70% indoles fraction, illustrate if
Without reextraction, indoles content is far not achieved 99%.
Comparative example 2：
Single extraction and reextraction are carried out by the raw material and condition of embodiment 1, the difference is that during reextraction
It is not added with water, indoles content is 91% in obtained heavy phase（When finger disregards wherein solvent content）, through solvent being distilled off to obtain the final product
91% indoles fraction, if illustrating that indoles content is also not achieved 99% if when reextraction is not added with water.
Comparative example 3：
Single extraction is carried out by the raw material and condition of embodiment 2, but without reextraction, indoles in obtained heavy phase
Content is 47.0%（When finger disregards wherein solvent content）, through water and solvent is distilled off up to 47.0% indoles fraction, explanation
If without reextraction, indoles content is far not achieved 85%.
Comparative example 4：
Single extraction and reextraction are carried out by the raw material and condition of embodiment 2, the difference is that during reextraction
It is not added with water, indoles content is 80.2% in obtained heavy phase（When finger disregards wherein solvent content）, through solvent being distilled off to obtain the final product
80.2% indoles fraction, if illustrating that indoles content is also not achieved 85% if when reextraction is not added with water.
Claims (4)
1. a kind of method of indoles Separation ＆ Purification, including following steps：Utilize the mixed methyl of indoles content 3~6%
Naphthalene is raw material, is mixed by a certain percentage with nonpolar solvent, then carries out single extraction with polar solvent to get to rich in indoles
Heavy phase and light phase containing a small amount of remaining indoles；0.1~0.7 times of water is added in heavy phase, then adds water with nonpolar solvent pair
Heavy phase carry out reextraction to get to 85% or more the product of indoles content when disregarding solvent content；Then to reextraction
The rectifying that obtained heavy phase carries out detaches to get to the thick indoles of polar solvent and 85% or more content without indoles；
Wherein, the polar solvent dosage is 0.3~1.0 times of indoles raw material, and the dosage of nonpolar solvent is indoles raw material
0.3~1.5 times；In the reextraction, the dosage of nonpolar solvent is 0.5~3.0 times of heavy phase.
2. a kind of method of indoles Separation ＆ Purification, including following steps：Utilize extraction β-first of indoles content 8~30%
Kettle Residual oil after base naphthalene is raw material, is mixed by a certain percentage with nonpolar solvent, then carries out single extraction with polar solvent,
Obtain the heavy phase rich in indoles and the light phase containing a small amount of remaining indoles；It is added 0.1~0.7 times of water in heavy phase, then with non-
The heavy phase of polar solvent pair plus water carries out reextraction to get to the heavy phase of 99% or more indoles content when disregarding solvent content；
Then to the obtained heavy phase of reextraction carry out rectifying detach to get to without indoles polar solvent and content 99% with
On indoles finished product；
Wherein, the polar solvent dosage is 0.3~1.0 times of indoles raw material, and the dosage of nonpolar solvent is indoles raw material
0.3~1.5 times；In the reextraction, the dosage of nonpolar solvent is 0.5~3.0 times of heavy phase.
3. the method for indoles Separation ＆ Purification described in claims 1 or 2, the polar solvent is triethylene glycol, ethylene glycol, dimethyl
Sulfoxide or ethanol amine；The nonpolar solvent is the kerosene of 160~200 DEG C of boiling point, 200#Solvent naphtha, normal octane or petroleum ether.
4. the method for indoles Separation ＆ Purification described in claims 1 or 2, the single extraction or reextraction are all 3~20
The counter-current extraction carried out in the extraction equipment of grade.
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| CN201410142972.4A CN103951604B (en) | 2014-04-11 | 2014-04-11 | A kind of method of indoles Separation ＆ Purification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151226A (en) * | 2014-08-26 | 2014-11-19 | 江苏万年长药业有限公司 | Extracting recycle method of indole from indole synthesis waste water |
| CN104876847B (en) * | 2015-05-09 | 2017-05-17 | 辽宁科技学院 | Method for extracting indole from methyl naphthalene fraction |
| CN106631967B (en) * | 2016-12-20 | 2019-03-29 | 北京化工大学 | A method of with indoles in Arquad extraction and separation washing oil |
| CN112279799B (en) * | 2019-07-26 | 2022-02-22 | 中石化南京化工研究院有限公司 | Method for preparing spice-grade indole by extraction crystallization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002068005A1 (en) * | 2001-02-26 | 2002-09-06 | The Procter & Gamble Company | Composition for aroma delivery with improved stability and reduced foaming |
| CN1746158A (en) * | 2004-09-09 | 2006-03-15 | 上海宝钢化工有限公司 | indole salt-adding extraction separation method |
| CN1746159A (en) * | 2004-09-09 | 2006-03-15 | 上海宝钢化工有限公司 | Indole separation and purification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04356458A (en) * | 1990-04-27 | 1992-12-10 | Kawasaki Steel Corp | Extraction of indoles |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002068005A1 (en) * | 2001-02-26 | 2002-09-06 | The Procter & Gamble Company | Composition for aroma delivery with improved stability and reduced foaming |
| CN1746158A (en) * | 2004-09-09 | 2006-03-15 | 上海宝钢化工有限公司 | indole salt-adding extraction separation method |
| CN1746159A (en) * | 2004-09-09 | 2006-03-15 | 上海宝钢化工有限公司 | Indole separation and purification |
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